Phosphate polymers

ABSTRACT

The present invention deals with the composition, and application of novel phosphate polymers. The polymeric compounds are useful as emulsifying agents, softening, anti-tangle, and conditioning agents for use in personal care applications due to their outstanding mildness.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention deals with the composition, and application ofnovel phosphate polymers. The compounds are useful as in personal careapplications due to their outstanding emulsification properties, andbecause they are polymeric do not penetrate skin, making themnon-irritating. The properties of these novel compounds that makes themwell suited for these applications is the fact that they are substantiveto fibers, hair and skin and also very mild to the skin and eyes andprovide protection from environmental factors like acid rain and otherpollutions which come in contact with hair and skin. The use of thecompounds results in several additional desirable properties heretoforeunattainable. This includes overcoming the problem of eye and skinirritation using traditional cationic conditioning agents.

2. Arts and Practices

The prior practices for providing softening, anti-tangle, andconditioning properties for use in personal care, textile and relatedapplications has been incorporation of quaternary compounds. Thesematerials have been used for many years despite some significantdrawbacks including irritation, negative impact on the aquaticenvironment, build up and yellowing of the substrate upon which they areapplied.

U.S. Pat. No. 5,162,472 to O'Lenick discloses free radical polymerswhich incorporate silicone into the backbone. While these materials havedesirable properties, they do not have an ionizable phosphate group inthe molecule.

The references cited herein are incorporated by reference to the extentapplicable. Ratios and percentages are by weight and temperatures areCelsius unless otherwise stated.

THE INVENTION Object of the Invention

It is the object of the current invention to provide a novel series ofanionic free radical polymers. The polymers are made byhomo-polymerization of the novel phosphate monomer or by polymerizationwith a variety of other vinyl containing free radical reactive monomers.The formation of a high molecular weight polymer results in lesspenetration of the skin by the compounds of the present invention and avery effective conditioner that remains on the surfact of the hair orskin where the conditioning agent is most effective.

It is another object of the current invention to provide a novel allylalkoxy phosphates used as an intermediate in the preparation of thecompounds of the present invention.

It is still another objective of the current invention to providepersonal care compositions which contain an effective conditioningamount of the compounds of the current invention. That effectiveconditioning concentration will vary from 0.1 to 20% of the composition.The compounds of the present invention have outstanding conditioningproperties when applied to hair and skin.

SUMMARY OF THE INVENTION

The present invention is directed to free radical polymers which containa phosphate group as one of the functional groups polymerized. Thecompounds of the invention are prepared by the free radicalpolymerization of a novel allyl phosphate monomer.

The phosphate functional allyl monomer is polymerized and subsequentlyused as the emulsification and conditioning agents for hair and skin.

The allyl alkoxy phosphate used to make the compounds of the presentinvention conform to the following structure:

(R)_(X)—P(O)—(OH)_(Y)

wherein;

R is CH₂═CH—CH₂—O—(CH₂CH₂O)_(S)—(CH₂CH(CH₃)O)_(t)—(CH₂CH₂O)_(u);

S, t and u are integers each independently ranging from 0 to 20;

x and y are each independently 1 or 2, with the proviso that x+y=3.

The compounds are made by the reaction of allyl alcohol alkoxylates,which are commercially available with a phosphating agent selected frompolyphosphoric acid or P₂O₅.

When polyphospohric acid is used the products are primarily compounds inwhich x is 1 and y is 2.

CH₂═CH—CH₂—O—(CH₂CH₂O)_(s)—(CH₂CH(CH₃)O)—(CH₂CH₂O)_(u)—H allyl alcoholalkoxylate

+PolyphosphoricAcid→CH₂═CH—CH₂—O—(CH₂CH₂O)_(s)—(CH₂CH(CH₃)O)_(t)—(CH₂CH₂O)_(u)P(O)—(OH)₂

When P₂O₅ is used the products are primarily compounds in which x is 2and y is 1.

CH₂═CH—CH₂—O—(CH₂CH₂O)_(s)—(CH₂CH(CH₃)O)_(t)—(CH₂CH₂O)_(cu)—H allylalcohol alkoxylate

+P₂O₅→(CH₂═CHCH₂—O(CH₂CH₂O)_(s)—(CH₂CH(CH₃)O)_(t)—(CH₂CH₂O)_(u))₂P(O)—(OH)

These allyl alkoxy phosphates are key materials to synthesis thepolymers of the present invention. The polymers conform to the followingstructure;

wherein;

R′ is

CH₂—O (CH₂CH₂O)_(s)—(CH₂CH(CH₃)O)_(t)—(CH₂CH₂O)_(u)—P(O)—(OH)₂

s, t and u are integers each independently ranging from 0 to 20;

e is an integer from 10 to 2,000.

The compounds of the current invention are prepared by the free radicalreaction of the allyl alkoxy phosphate containing monomer.

The compounds of the current invention conform to the following genericstructure;

wherein;

R″ is selected from the group consisting of CH3 and H;

a is an integer from 1 to 100;

b, c, and d are integers ranging from 0 to 100;

R¹ is

—CH₂—O—(CH₂CH₂O)_(s)—(CH₂CH(CH₃)O)_(t)—(CH₂CH₂O)_(u)P(O)—(OH)₂

s, t and u are independently integers ranging from 0 to 20;

R² is —C(O)—O⁻M⁺

M is selected from H, Na, K, Li, and NH 4;

R³ is

R⁴ is

R¹⁰, R¹¹ and R¹² are selected from H, methyl and ethyl;

R⁵ is —C(O)—NH₂

R⁶ is

—C(O)—N(H)—(CH₂)_(q)—SO₃ ⁻M⁺

q is an integer ranging from 1 to 5.

The compounds of the current invention are prepared by the free radicalreaction of a meadowfoam ester containing monomer and other monomersselected from the following;

R¹ is derived from the monomer conforming to the following structure;

CH₂═CH—CH₂—O—(CH₂CH₂O)_(s)—(CH₂CH(CH₃)O)_(t)—(CH₂CH₂O)_(u)P(O)—(OH)₂

s, t and u are independently integers ranging from 0 to 20;

R² is derived from the following monomer CH₂αCH—C(O)—O⁻M⁺

Acrylic acid and methacrylic acid is available from Dow. R³ is derivedfrom the following monomer;

Vinyl pyrrolidone is available commercially from BASF.

R⁴ is derived from the following monomer;

R¹⁰, R¹¹ and R¹² are selected from H, methyl and ethyl;

These monomers are available from CPS Corporation.

R⁵ is derived from the following monomer CH₂═CH—C(O)—NH₂

Acrylamide is available from Dow Chemical.

R⁶ is derived from the following monomer;

CH₂═CH—C(O)—N(H)—(CH₂)_(q)—SO₃ ⁻M⁺

These materials are available from Lubrizol Inc.

These materials are reacted in a solvent, typically water under theinfluence of a free radical catalyst. Free radical polymerization iswell known to those skilled in the art.

PREFERRED EMBODIMENTS

In a preferred embodiment R³, R⁴, R⁵ and R⁶ are all zero and R¹ and R₂are independently integers ranging from 1 to 100.

In a preferred embodiment R², R⁴, R⁵ and R⁶ are all zero and R¹ and R₃are independently integers ranging from 1 to 100.

In a preferred embodiment R², R³, R⁵ and R⁶ are all zero and R¹ and R₄are independently integers ranging from 1 to 100.

In a preferred embodiment R², R³, R⁴ and R⁶ are all zero and R¹ and R₅are independently integers ranging from 1 to 100.

In a preferred embodiment R², R³, R⁴ and R⁵ are all zero and R¹ and R₆are independently integers ranging from 1 to 100.

In a preferred embodiemnt x is 1 and y is 2.

EXAMPLES Raw Materials

Allyl Alcohol Alkoxylates

These compounds conform to the following structure:

CH₂═CH—CH₂—O—(CH₂CH₂—O)_(s)—(CH₂CH(CH₃)CH₂—O)_(t)—(CH₂CH₂—O)_(u)—H

Example Number s t u 1 0 0 0 2 0 1 0 3 4 0 0 4 7 0 0 5 10 0 0 6 20 0 0 74 7 10 8 7 4 20 9 10 20 4 10 20 10 7 11 20 20 20 12 7 7 7

These materials are items of commerce available commercially fromSiltech Corporation Toronto Ontario Canada, and Pelron corporationChicago Ill.

Phosphation

Phosphating Agents

Polyphosphoric Acid (PPA) is 115% phosphoric acid. When used as aphosphating agent in gives more mono ester than the phosphoruspentoxide.

Phosphorus pentoxide is P₂O₅. It is more aggressive in phosphation andresults in more diester.

The phosphates of this invention can be prepared by reacting thehydroxyl group with a suitable phosphating agent. Preferred phosphatingreagents are polyphosphoric acid and phosphorus pentoxide.

GENERAL PROCEDURE

The specified amount of allyl alkoxy compound (example 1-12) is added toa suitable reaction vessel. The specified amount of eitherpolyphosphoric acid or phosphorus pentoxide is charged to under goodagitation over a 2 hr. period. The exothermic reaction raises thetemperature of the mixture to about 70 C. After 1 hour slowly raise thetemperature to 100 C and hold 2-4 hours.

Allyl Alkoxylate Polyphosphoric Acid Example Example Grams Grams 13 157.0 98.0 14 2 116.0 98.0 15 3 233.0 98.0 16 4 365.0 98.0 17 5 497.098.0 18 6 937.0 98.0 19 7 1086.0 98.0 20 8 1481.0 98.0 21 9 1853.0 98.022 10 1835.0 98.0 23 11 2977.0 98.0 24 12 1499.0 98.0 25 1 57.0 47.6 263 233.0 47.6 27 5 497.0 47.6 28 7 1086.0 47.6 29 8 1481.0 47.6 30 91853.0 47.6 31 10 1835.0 47.6 32 11 2997.0 47.6

Preparation of Phosphate Homo-polymers Examples 33-52

General Polymerization Procedure;

The polymerization of the allyl phosphate compound is achieved byutilizing free radical catalyst in a low oxygen containing solvent, mostcommonly water. The water is deionized and sparged with nitrogen toremove dissolved oxygen contained therein immediately prior to use.Then, the specified amount of the treated de-ionized water is added to asuitable glass vessel. Most commonly, 50 to 80% of the total weight ofthe batch is water. The specified amount of the specified monomers arethen added under agitation. Nitrogen is continuously sparged and thetemperature is raised to about 50 C. Once the temperature has reached 50and the nitrogen has been bubbled through the reaction mass for thirtyminutes, a free radical initiator is added. Many peracids, liket-butyl-perbenzoate, t-butyl-hydroperoxide and inorganic free radicalinitiators like stannic chloride can be used. The preferred initiator isazobisisobutylnitrile. The reaction is exothermic and cooling is used tokeep the temperature below 90 C. The molecular weight is monitored byviscosity and both increase as the reaction continues.

Romopolymers Example 33

To the 5,000 grams of deionized water, which has just been sparged withnitrogen for 30 minutes, is added the specified amount 5,000 grams ofthe specified allyl phosphate monomer Ex #13 under good agitation andnitrogen sparge. The temperature is raised to about 50 C. Once thetemperature has reached 50 and the nitrogen has been bubbled through thereaction mass for thirty minutes, 0.05% by weight of batch ofazobisisobutylnitrile. The catalyst may be optimally added in smallerincrements of one quarter of the total needed waiting 30 minutes betweenadditions. The viscosity will raise as the polymerization occurs. Thetemperature raises to about 90 C and is cooled with cooling water asneeded to prevent the temperature from reaching 90 C. The molecularweight is controlled by viscosity. When the desired viscosity isachieved, air is bubbled through the vessel to quench the polymer. Thedesired polymer is used as prepared.

Examples 33-52

Example 33 is repeated only substituting the allyl phosphate r forexample 13 used in example 49.

Example Allyl Phosphate Example 33 13 34 14 35 15 36 16 37 17 38 18 3919 40 20 41 21 42 22 43 23 44 24 45 25 46 26 47 27 48 28 49 29 50 30 5131 52 32

Preparation of Phosphate Hetero-polymers

The vinyl containing compounds that were homo-polymerized in example33-52 can be polymerized with other vinyl containing, free radicalreactive monomers. These so-called heteropolymers have addedfunctionality and provide unique properties.

Class 1 Vinyl Phosphate Compounds Examples 13-32 Class 2 Vinyl AminoCompounds Examples 53-57

Example R¹⁰ R¹¹ R¹² 53 Methyl Methyl Hydrogen 54 Methyl Methyl Methyl 55Ethyl Methyl Hydrogen 56 Ethyl Methyl Methyl 57 Ethyl Ethyl Methyl

Class 3 Vinyl Anionic Materials Examples 58-61

CH2═CH—C(O)—N(H)—(CH₂)_(q)—SO3⁻M⁺

Example q M 58 3 H 59 4 H 60 3 Na 61 3 K

Class 4 Vinyl Carboxylic Compounds Example 62

Acrylic Acid CH2═CH—C(O)—OH

Class 5 Vinyl Lactones Example 63

Class 6 Vinyl Amides Example 64

Acrylamide CH2═CH—C(O)—NH2

Preparation of Hetero-polymers Examples 65-93

General Polymerization Procedure;

The polymerization of the vinyl containing meadowfoam esters is achievedby utilizing free radical catalyst in a low oxygen containing solvent,most commonly water. The water is deionized and sparged with nitrogen toremove dissolved oxygen contained therein immediately prior to use.Then, the specified amount of the treated de-ionized water is added to asuitable glass vessel. Most commonly, 50 to 80% of the total weight ofthe batch is water. The specified amount of the specified monomers arethen added under agitation. Nitrogen is continuously sparged and thetemperature is raised to about 50 C. Once the temperature has reached 50and the nitrogen has been bubbled through the reaction mass for thirtyminutes, a free radical initiator is added. Many peracids, liket-butyl-perbenzoate, t-butyl-hydroperoxide and inorganic free radicalinitiators like stannic chloride can be used. The preferred initiator isazobisisobutyl-nitrile. The reaction is exothermic and cooling is usedto keep the temperature below 90 C.

The molecular weight is monitored by viscosity and both increase as thereaction continues.

Example 65

To the specified number of grams (5,000 Gm.) of deionized water, whichhas just been spargred with nitrogen for 30 minutes, is added thespecified amount (4,200 grams) of Class 1 monomer (Ex #13). Next add thespecified amount (0 grams) of Class 2 monomer (Ex #53) followed by thespecified amount (0 grams) of Class 3 monomer (Ex #58) followed by thespecified amount (0 grams) of Class 4 monomer (EX #64) followed by thespecified amount (0 grams) of Class 5 monomer (Ex #63) followed by thespecified amount (0 grams) of Class 6 monomer (Ex #64), under goodagitation and nitrogen sparge. The temperature is raised to about 50 C.Once the temperature has reached 50 and the nitrogen has been bubbledthrough the reaction mass for thirty minutes, the specified amount ofthe specified catalyst (azobisisobutylnitrile) is added. The catalystmay be optimally added in smaller increments of one quarter of the totalneeded waiting 30 minutes between additions. The viscosity will raise asthe polymerization occurs. The temperature raises to about 90 C and iscooled with cooling water as needed to prevent the temperature fromreaching 90 C. The desired polymer is used as prepared.

Examples 66-93

The above procedure is repeated only substituting the specified amountand type of monomer, catalyst and water specified.

Example 66 Example 67 Example 68 Example 69 Class 1 Ex # 14 Ex # 15 Ex #16 Ex # 17 4,200 Gm. 3,860 Gm. 12,747 Gm. 1,714 Gm. Class 2 Ex # 53 Ex #54 Ex # 55 Ex # 56 157.0 Gm. 171.0 Gm. 185.0 Gm. 216.0 Gm. Class 3 Ex #58 Ex # 59 Ex # 60 Ex # 61 193.0 Gm. 207.0 Gm. 215.0 Gm. 231.0 Gm. Class4 Ex # 62 Ex # 62 Ex # 62 Ex # 62 72.0 Gm. 0 Gm. 0 Gm. 0 Gm. Class 5 Ex# 63 Ex # 63 Ex # 63 Ex # 63 110.0 Gm. 1,100 Gm. 110.0 Gm. 0 Gm. Class 6Ex # 64 Ex # 64 Ex # 64 Ex # 64 158.0 Gm. 1,580 Gm. 0 Gm. 0 Gm. Water5,000 Gm. 10,000 Gm. 20,000 Gm. 5,000 Gms

Catalyst These examples used 0.05% by weight of batch ofazobisisobutylnitrile

Example 70 Example 71 Example 72 Example 73 Class 1 Ex # 18 Ex # 19 Ex #20 Ex # 21 13.5 Gm. 15.4 Gm. 67.8 Gm. 50.4 Gm. Class 2 Ex # 53 Ex # 54Ex # 55 Ex # 57 157.0 Gm. 171.0 Gm. 185.0 Gm. 216.0 Gm. Class 3 Ex # 58Ex # 58 Ex # 58 Ex # 58 0 Gm. 0 Gm. 0 Gm. 0 Gm. Class 4 Ex # 62 Ex # 62Ex # 62 Ex # 62 0 Gm. 0 Gm. 0 Gm. 0 Gm. Class 5 Ex # 63 Ex # 63 Ex # 63Ex # 63 0 Gm. 110.0 Gm. 1,100 Gm. 11.0 Gm. Class 6 Ex # 64 Ex # 64 Ex #64 Ex # 64 0 Gm. 0 Gm. 0 Gm. 0 Gm. Water 250 Gm. 600 Gm. 3,000 Gm. 150Gm.

Catalyst These examples used 0.05% by weight of batch ofazobisisobutylnitrile

Example 74 Example 75 Example 76 Example 77 Class 1 Ex # 22 Ex # 23 Ex #24 Ex # 25 4,200 Gm. 3,860 Gm. 12,747 Gm. 1,714 Gm. Class 2 Ex # 53 Ex #55 Ex # 56 Ex # 57 0 Gm. 157.0 Gm. 171.0 Gm. 185.0 Gm. Class 3 Ex # 58Ex # 58 Ex # 58 Ex # 59 0 Gm. 0 Gm. 193.0 Gm. 207.0 Gm. Class 4 Ex # 62Ex # 62 Ex # 62 Ex # 62 0 Gm. 0 Gm. 0 Gm. 72.0 Gm. Class 5 Ex # 63 Ex #63 Ex # 63 Ex # 63 0 Gm. 0 Gm. 0 Gm. 0 Gm. Class 6 Ex # 64 Ex # 64 Ex #64 Ex # 64 0 Gm. 0 Gm. 0 Gm. 0 Gm. Water 4,200 Gm. 5,000 Gm. 15,000 Gm.2,500 Gm.

Catalyst These examples used 0.05% by weight of batch ofazobisisobytylnitrile

Example 78 Example 79 Example 80 Example 81 Class 1 Ex # 26 Ex # 27 Ex #28 Ex # 29 1,355 Gm. 15,415 Gm. 6,789 Gm. 5,043 Gm. Class 2 Ex # 53 Ex #54 Ex # 55 Ex # 56 216.0 Gm. 1,570 Gm. 1,710 Gm. 1,850 Gm. Class 3 Ex #58 Ex # 59 Ex # 60 Ex # 61 215.0 Gm. 231.0 Gin. 193.0 Gm. 207.0 Gm.Class 4 Ex # 62 Ex # 62 Ex # 62 Ex # 62 0 Gm. 0 Gm. 0 Gm. 0 Gm. Class 5Ex # 63 Ex # 63 Ex # 63 Ex # 63 110.0 Gm. 110.0 Gm. 110.0 Gm. 1,100 Gm.Class 6 Ex # 64 Ex # 64 Ex # 64 Ex # 64 0 Gm. 0 Gm. 0 Gm. 158.0 Gm.Water 2,000 Gm. 22,000 Gm. 10,000 Gm. 10,000 Gm.

Catalyst These examples used 0.05% by weight of batch oft-butyl-hydroperoxide (Lucidol TBHP-70-X)

Example 82 Example 83 Example 84 Example 85 Class 1 Ex # 30 Ex # 31 Ex #32 Ex # 31 4,200 Gm. 3,860 Gm. 12,747 Gm. 1,714 Gm. Class 2 Ex # 55 Ex #54 Ex # 53 Ex # 57 0 Gm. 0 Gm. 0 Gm. 0 Gm. Class 3 Ex # 58 EX # 58 Ex #58 Ex # 58 0 Gm. 0 Gm. 0 Gm. 0 Gm. Class 4 Ex # 62 Ex # 62 Ex # 62 Ex #62 0 Gm. 0 Gm. 0 Gm. 0 Gm. Class 5 Ex # 63 Ex # 63 Ex # 63 Ex # 63 4,200Gm. 110.0 Gm. 30,000 Gm. 100.0 Gm. Class 6 Ex # 64 Ex # 64 Ex # 64 Ex #64 0 Gm. 0 Gm. 0 Gm. 0 Gm. Water 10,000 Gm. 5,000 Gm. 55,000 Gm. 1,000Gm.

Catalyst These examples used 0.07% by weight of batch oft-butyl-hydroperoxide (Lucidol TBHP-70-X)

Example 86 Example 87 Example 88 Example 89 Class 1 Ex # 31 Ex # 22 Ex #23 Ex # 24 135.5 Gm. 154.1 Gm. 67.9 Gm. 50.4 Gm. Class 2 Ex # 53 Ex # 53Ex # 53 Ex # 53 1,570 Gm. 0 Gm. 0 Gm. 0 Gm. Class 3 Ex # 68 Ex # 69 Ex #60 Ex # 61 0 Gm. 1,930 Gm. 0 Gm. 0 Gm. Class 4 Ex # 62 Ex # 62 Ex # 62Ex # 62 0 Gm. 0 Gm. 720 Gm. 0 Gm. Class 5 Ex # 63 Ex # 63 Ex # 63 Ex #63 0 Gm. 0 Gm. 0 Gm. 1,100 Gm. Class 6 Ex # 64 Ex # 64 Ex # 64 Ex # 64 0Gm. 0 Gm. 0 Gm. 0 Gm. Water 1,000 Gm. 1,000 Gm. 1,000 Gm. 2,000 Gm.

Catalyst These examples used 0.07% by weight of batch of t-butylperbenzoate

Example 90 Example 91 Example 92 Example 93 Class 1 Ex # 32 Ex # 31 Ex #30 Ex # 29 420.0 Gm. 386.0 Gm. 1,274 Gm. 171.4 Gm. Class 2 Ex # 56 Ex #55 Ex # 56 Ex # 57 216.0 Gm. 2,160 Gm. 2.16 Gm. 2,160 Gm. Class 3 Ex #58 Ex # 59 Ex # 60 Ex # 61 0 Gm. 0 Gm. 0 Gm. 0 Gm. Class 4 Ex # 62 Ex #62 Ex # 62 Ex # 62 0 Gm. 0 Gm. 0 Gm. 0 Gm. Class 5 Ex # 63 Ex # 63 Ex #63 Ex # 63 110.0 Gm. 1,100 Gm. 11.0 Gm. 0 Gm. Class 6 Ex # 64 Ex # 64 Ex# 64 Ex # 64 0 Gm. 0 Gm. 0 Gm. 0 Gm. Water 500 Gm. 1,000 Gm. 5,000 Gm.10,000 Gm.

Catalyst These examples used 0.05% by weight of batch of t-butylperbenzoate

Applications Examples

The polymers of the present invention are very substantive conditionersto the hair and are surprisingly mild to the skin and eyes. Eyeirritation is a major concern in the formulation of personal careproducts, particularly when working with quats. Primary eye irritationwas tested using the protocol outlined in FHSLA 16 CFR 1500.42. Theproducts were tested at 25% actives. The results were as follows;

What is claimed is:
 1. A polymer conforming to the following structure:

wherein; R² is—CH₂—O—(CH₂CH₂O)_(s)—(CH₂CH(CH₃)O)_(t)—(CH₂CH₂O)_(u)—P(O)—(OH)₂ s, t andu are integers each independently ranging from 0 to 20; e is an integerfrom 10 to 2,000.